Document JLzxpmwjzwJkBqBnmKoK8RRe

E. I. DU PONT DE NEMOURS & COMPANY PIGMENTS DEPARTMENT 256 VANDERPOOL STREET NEWARK, NEW JERSEY KH-46-54 Copy No. t r/ RETURN TO JACKSON LABORATORY FILE ROOM NEWARK PLANT PIGMENT COLOR RESEARCH REPORT Pinal Report General Patent Survey - Phthalocyaaine Pigments. Period Covered: May 1 - July 25, 1946 *&***& a NJaeee FILE: 223.4 DATE: 8-12-46 N39977 Serial So. KM-46-54 f- Copy No Copy to: #1 - Numerical Pile 2 - Research Office (223.4) 3 - Library Pile (223.4) 4 - Dr. J* E, Booge, Newport 5 - Dr. W. p, Spengemaa, Newark 6 " Hr. A. Siegel, Newark 7 - Bn. B, H. Perkins, Newark 8 - Dr. P. P. Ehrich, Newark 9 - Mr. A. J Stratton, Newark 10 - Dr. D. B* Killian, Newark 11 "Mr. J. P. Hancock, Wilmington 12 " Orchem Patent Service, Jackson Lab. 13 - Extra 14 ~ " NEWARK PLANT PIGMENT COLOR RESEARCH REPORT Pinal Report Title: GENERAL PATENT SURVEY - PHTIIALOCYANINE PIGMENTS. Period Covered: MAY 1 JULY 25, 1948 SUBMITTED BY: A. J. STRATTON APPROVED BY: D. B. KILLIAN DATS SUBMITTED: 7-26-45 DATE ISSUED: 8-12-46 N39977.01 DUP050150236 PHfHALOGYAK 1H3S PISMEHTE * SBSBR/fi SURVEY :an?BODi?o?ios;, Ihthalocyanine pigments have been sole la. the United spates by the DuPont Company since about 193 5 The manufacture of the pig ment has, up to the present time* 'baen carried out exclusively yy the Organic ChsaicaXs Department* Howevert the Pigruonts Department lave used tha pigzant as a seal-finished, product in the preparation of numerous modifications for special usree# Baring this period, extensive studies have been carried on in the laboratories of Orchea and of the Pigments Department and numerous reports sro in ho found in the files 'of each laboratory* These reports Xuolude a thorough review of the historical aspects of the development gad -th Lv **111 -not be repeated herein0 For a brief review thereof, reference is made to Never!': report in/~46>70 Recently, e decision has been retrieved, to carry on research leading tip to the full scale manufacture of ehthalacyamine pigments within the Pigments.Department* This research ban now progressed sub stantially to- the point of pilot plant operation, and, although numerous patent surveys have been made by the Jackson Laboratory of Orehem and the patent situation is fairly well understood by those interested in it, no such survey of the art has heretofore been made at Newark and it seems highly desirable to make such a complete survey from our own point of view* With these facts in mind, the patent, art has been thoroughly reviewed with particular reference to the preferred.process at Newark, but* a brief summary has also been included of the whole ohthalooyanine art,in anticipation of a need for broadening this survey et some future d&ter -:COPr. OF -fEE KSVIBW AflD SOURCES: As pointed out above, this review has been directed particularly towards one process now contemplated for use at Newark but has also included a rather careful search of th art on the synthesis and finishing of copper phthalocyanine and its chlorinated derivatives. A somewhat less careful survey has been made of use patents and of patents covering other metal phthalocyanines as well as products in which the benzene nuclei contain various substituents* Although these latter products are not contemplated for manufacture at the present time, it seems'highly probable that some of them may be of interest for future study* DUP050150237 As to the sources of this review, an nttempt has boon mads to inspect all 0..S* and British phthalocyanine patents 'which have been Issued to date< It is believed that all such tLS* patents are available in the Newark Library and that substantially si? British patents are also available To insure this point, a careful search -.fas cade of Ohomlcal Abstracts and,likewise, of the Jackson Laboratory patent files- /- less careful search has been made of the Trench, Cevcian, and Swiss patents on this subject, with considerable depends-.ice placed upon the Abat-act Journals for. information with respect to many of these foreign p-.teats* However, since we are primarily concerned, with domination, thasc patents are of minor importance in this search* PROCESS; 2a&s&i2_&OiU\s.. There are two .ftmlomeataU.;/ different processes which fc.ave been widely used for the manufacture of copper fhthslocyaninIn one, phtkaloaitrile is heated with a coppor salt to about 180C at which point a vigorous, exothermic reaction sterfcs and'goes tc.ccplstion in a relatively short times Because of the extremely vigorous nature of this reaction, It has been difficult to control and the addition of inert material, either salt, such as sodium chloride or high boiling liquid,such as kerosene or trichlorbeazens, has been common practice,. This process has been used largely heretofore by Orehem and Is still being used for the standard copper phthalocyanine pigment CBT~X72-B) which Is sold by the Pigment,:; Department, The other common process involves the reaction of phfc.ialic anhydride, urea and a copper salt in the presence of certain, catalysts at temperatures in the order of 200G,, Although this reaction may be carried out as a melt, which eventually sets up to a solid as the pig~ meat is formed, it has been much mors successfully handled in the presence cf a liquid diluent such as kerosene or trlehlorbenzene.' It is this process using a purified grade of kerosene as the diluent,and ammonium molybdate as the catalyst,which Kewark proposes to adopt* However, it is known that this process results in the formation of a. chlorine-free blue which has certain undesirable characteristics,' namely a loss of strength in the presence of hydrocarbon solvent*_^-- for many uses* It is entirely satisfactory as a raw materiartfor the subsequent manufacture of chlorinated green phthalocyanine and will be manufactured for this use,. To manufacture a grade of phthalocyanine blue which is stable in the presence of hydrocarbon solvent, it is proposed to resort to the substitution of a minor proportion, about 15# to 20$, of 4-chlor ihthallc acid for an equivalent amount of the phthalic anhydride used in the reaction* This results in the forma tion of a blue phthalocyanine containing approximately 4$ of chlorine* DUP050150238 The process proposed for vise at !!?mrk is substantially identical with that, used by 1*0* I* in England for Boat of their phthalocyanin manufacture, They aernrfaeturc the chlorine-free grade under the designation KJSonestr&X* Blur B and the grad con taining chlorine under tha designation "ikmastral** Bins 13 'ifeere the designation "Blue 0" and ''Blue LB" are used throughout this report, they will have meanings similar to those used by I,,C,I, The only pbthalocyanlne green marketed la this country has been a highly chlorinated copper phthaloeyanine containing between 14 and 15 atoms of chlorine per molecule of copper phthalocyaviJjae (approximately 48% chlorine} The only process practiced commercially to our knowledge has involved the ehlo?ination of Blue B suspended in the eutectic melt of anhydrous aliuain.ua; chloride arid a odium chloride* It is an. expensive orocass and difficult to control* Hewerk does not propose to use this process but will instead use sulfur dichlorlde as a combined carrier and chlorinating agent wo.rklng under pressure and at relatively high temperatures, The details of the process are rather complex, and it has been practiced only on s laboratory scale, but it has shown much promise of substantial economy because of the relative ease with which the sulfur dichloride can be recovered for reuse, are In the past,all commercial processes of which we/aware. for the manufacture of phthalocyanina pigments involvedthe "so-called" acid pasting steps,in which the pigment is dissolved in highly concentrated sulfuric acid, or, in the case of the green, in a mixture of sulfuric acid and chlorsulfonic acid, and the pigment reprecipitated therefrom by diluting the acid solution with water* More recently, Qrchera has developed a "so-called" salt milling process in which the pigment and a relatively large amount of an inorganic salt,such as sodium chloride or sodium sulfate,are ball milled together for a substantial period of tine followed by extraction of the water soluble salt and isolation of the pure pigment. This process is under development for commercial operation by both Orchem and the Imperial Chemical Industries in England,. The Pigments Department does not propose to use either of these processes but have developed a new process which we have called "Solvent Milling", In this process,the pigment, either in the dry fora (which may be a purified or simply a dried out crude), or in the form-of a kerosene-containing filter cake from the synthesis step,is ground in a ball mill with a solvent such as kerosene or mineral spirits. After a suitable milling cycle (the unproven goal on a plant scale is a maximum of 48 hours), the mill charge will be dumped, separated from the solvent (probably by steam distillation) and extracted for the removal of any impurities such as the residual impurities from the synthesis stage#or impurities resulting from abrasion or corrosion of tha grinding device. DUP050150239 In the ease of the grasn, it seems desirable to add approximately equal quantities of an Inorganic salt such as sodium sulfate to the grind,end it seems necessary to use only hydrocarbon solvent for the liquid portion. The presence of even small amounts of water appears definitely harmful to the greens. On the other hand, In the case of i.fco blue, it has been possible to get entirely satisfactory grinding with alcohols or other --ater soluble solvents containing up to as high 'as 4C{ of . water, Sven crater alone has enabled a substantial improvement in strengthfSlthougKto date, the desired strength has not been obtained in this medium# Sines grinds >tsAo At the presence of a appreciable amount of weter suffer from a substantial corrosion problem in steel ball mills, the proposed process is at present restricted to the use of a hydrocarbon solvent. Finally* it should be noted that the best results have been obtained when, the grinds were made in the presence of an organic acid such es naphthenic ac.lri or oleic p.cidffollcuved by steam distillation in the presence of certain treating agents, , notably a combination of the I'M Ester and glyceryl mono , > riciaoleats, the preferred agents nave not been selected with certainty at this time,but it seams quite definite that some agent will be necessary in these steps# BPaMAHI & COflCLPSIOHS? lo There is no patent containing a product claim on copoer phthalocyanine as such and none is possible at this time# 2o There is a patent containing a product claim covering monochlor copper phthalocyanine, It is assigned to I,.Col, and licensed to DuPont, 3, All practical processes for the synthesis of copper phthalocyanine are covered in patents either owned by or licensed to DuPont# 40 All important process patents are believed to be valid and to b rather universally respected in the industry# 5 The process for the manufacture of Blue LB is disclosed but not specifically claimed aside from the general process coverage# Copper Phthalocyanin^ D^een_ 1, A presumably strong product patent covering the highlychlorinated copper phthalocyanine is owned by General Aniline but licensed to DuPont outside of the DuPont - General CPC agreement# This is a non-exclusive license and, in the event that all of General's patents are thrown open to license by the Alien Property Custodian, the product might become available to our competitorst. DUP050150240 Coplea tot #1 - numerical File 2 - Research Offloe (223.4) 3 - Library File (223.4) 4 - Or. <J. E. Booge, Newport 5 - Or. V. F. Spengenian, Newark 6 - Mr. A. Siegel, Newark T * Dr. B. H. Perkins, Newark Dr. F. F. Ehrich, Newark Mr A. J. Stratton, Newark Or. 0. B. Killian, Newark Mr. 2. P. Hancock, Wilmington Orchea Patent Service, Jackson Lab0 Extra ft 6UPPImm$i TO EK-46-54 - CENER&L PATENT SURVEY- iYAKINB PIGMENTS To be attached to page 5 of the report. Sinoo this report was issued on August 12, 1946 attention has been oallsd to an orror in the statement m page 5 that "There io no basic product olaia on metal-free phth&locyanino" It has been pointed out that claim 16 of U.S. 2,000,052, although eoTering a product made by a different process than that commonly employed in the manufacture of metal-free phthalocyanlne, nevertheleee dominates metal-free phthalocyanlne and is not limited to thO process disclosed. Accordingly, the statement quoted above should be changed to read "Claim 18 of U.S; 2,000,052 is considered a valid product claim for arirtalfrae phthalocyanlne. This XCX patent is available for the use of Du Pont". a Wt/j STRATTON io/ii/4 APPROVED* i DU P050150241 * J However* there appears to he m reason to believe that our present ' license will he disturbed* 2c Both or&ctical processes fop the aauufecturs of copper ohthalocyanlne green, namely the aluminum chloride 3odium chloride melt and the sulfur diehloride processes, are covered by presumably valid oatents owned by DuPont,so that regardlons of our lack -of . control of the product itself, our patent position seems quite ` strong* 1.there is no basic product claim on icotal-free phfchalGcyantne* 2? The commonly known praotleal processes for the manufacture of metal-free phthalocyanlns arc covered by patents either owned by or licensed to DuPont* I* There is no basic oatent covering the anid-pasting procedure and none is possible at present* However, there are numerous patents on various details of the acid-pasting and subsequent drowning steps including the use of treating agents in the drowning step* Hot all of these patents are available for the use of DuPont,but it is believed that there are none which will hamper any operations now contemplated* Since we do not propose to use acid-pasting la the Pigments Department* it is certain that none of them will disturb our operation* 2. DuPont owns a patent on the salt milling process which was issued quite recently but it is our opinion that this oatoat is quite weak in view of numerous references to similar processes in the art* 3: We have found no specific disclosures of solvent milling as we propose to practice it,and it is believed to be a patentable process* However, this will be made the subject of a separate report* 4* Miscellaneous Finishing Steps* It is believed tbat our process may possibly be in conflict with O.S* 2,138,049 and 2,268|144 (owned by Harmon) if any of the solvent remains after steam distillation to be removed in the oven* However, negotiations which will give DuPont rights under these patents have been initiated at the present time. We are informed by representatives of Orchem that the use of the TEA C_9 Ester is under some patent restrictions* However, we are also ^ informed by them that they have obtained licenses for the use of this material and it, therefore, is now open to our use* Ho effort has been made to locate tho patent involved. I 'feV .. DUP050150242 ^a The general field of the use of various types of treating agents in the manufacture of pigments is one in which there ere a great many patents hut substantially all of these patents are of very limited scope# Ho extended search has aeon made in this" field at the present time# However, the field 'ass been broadly covered in previous searches made at Hewark and we feel confident.in the opinion that there are no insurmountable patent bars# Some of the more important patents in this group will be discussed in connection with the detailed description of the orto fiSEAn@,lL3g^ In the following discussion of the patent art two main divisions will be recognised# The first will discuss in soma detail those patents believed to be directly pertinent to perationsof the DuPont Company In the manufacture of phthalocyanine pigments, with emphasis -being laid on those which are particularly concerned with the operations of the Pigments Department# This group of patents will be further sub-divided under the four topics used above in the' summary of the art# The second main division will include in a much less detailed fashion substantially all of the remaining U*S patents in the phthalo cyanine field# It will also include many of the British patents and some reference will be made to other foreign patents# In addition to the four main sub-divisions referred to above, it will also include references to other metal phthalocyanines, to some patents on uses of phthalocyanines and to a large group of patents concerned with pro ducts in which there are substituent groups on the benzene rings of the phthalocyanine molecule# This last group of patents will be listed by descriptive title only for the most part and are being included only for a ready reference.in the future# DUP050150243 -. - -"VV*- ,,-s;*rws 7 A, PATENTS OF MAJOR XHtgORTAHCE la Popper PhtSmlocvanlna U.S, 2,000,051, issued 5-7-55 to Thorpe, Linstsad & Thomas of I.C.I. This is the first phthalocyanine patent in the United States and covers a process of reacting o-cyanobenz&mid with a metal or a metal compound under the influence of heat* A large number of metals including magnesium, copper and tin are disclosed as effective. Their use as pigments is disclosed as well as the process of acid pasting to obtain them in a fine state of subdivision. The possibility of re moving some metals such as magnesium through the use of concentrated sulfuric acid to give a metalrfree compound is recognised. There Is no clear recognition of the structure of plitha?.cnyanlnes as now accepted in this patent, but It Is very closely approximated. The disclosure of this patent with respect to the compounds formed is basic to the whole phthalocyanine industry in the United States* However, the process is not currently used and there are no product claims independent of the process because of a prior disclosure in the literature. U.S. 2,129,013, issued 9-6-38 to LInstead s Dent of I.C.I. When phthaldnitrile and cupric chloride are heated together above about 200C, the resulting product is copper monochioro phthalo cyanine. When cuprous chloride is used in place of cupric chloride, the product still contains chlorine but to a considerably lesser degree. The use of inert solvent is disclosed. Claim 5 covers copper monochlore phthalocyanine as a new product. U.S. 2.,197,458, issued 4-16-40 to Wyler of I.C.I. This patent covers broadly the phthalia anhydride/urea fusion process, wherein phthalie anhydride, urea and a metal salt such as cupric chloride are heated to a temperature in the order of 20CWC., whereby a solid pigmentary product is formed. The use of substituted phthalie anhydride,as well as the use of free acid, diammonium salts and certain other derivatives,is disclosed. The use of boric acid or ammonium sulfamate is recommended to improve yield and to prevent frothing. There is recognition of improved yields resulting from add ing the urea to a molten mixture of the phthalie anhydride and to the metal salts. There is no disclosure of the use of a liquid diluent or solvent. This patent Is basic for the process proposed for use at Newark. U.S. 2,197,459, issued 4-16-40 to Wyler of I.C.I. A phthalocyanine containing tin Is obtained by the use of the phthalie anhydrlde/urea fusion process of tJ.S. 2,197,458 in the presence of suitable tin salts. The patent discloses,but does not claim,the preparation of a metal-free compound by the demetallization of the tin containing phthalocyanine through solution in concentrated sulfuric acid. DUP050150244 8 It discloses, but does not claim, the use of kerosene or other High boil ing organic liquids as a diluent in the reaction. The di solostore of the use of kerosene is Important to us but there is no protection. Otherwise, there is no direct interest to Newark at the moment but it is of direct interest to Orehem in their manufacture of a co-salt milled copper and tin dlchloride phthaloeyanine, It is of potential Interest to both departments as a possible route for the manufacture of metal free phthalooyanine. Such a process Is now used by I.C.I, U.S. 8,214,47*?, issued 9-10-40 to Riley of 1.0,1. The efficiency of the phth&lic anhydride/urea fusion process is materially increased through the use of certain salts of metals of groups 5 and 6 of the periodic tables as catalysts for the reaction. Anmonium molybdate is the preferred salt and is used in very small amounts. We propose to us this prooess at Newark. U.S.Application, Serial #629,921, Application Date 11-20-45 by A. Siegel, assigned to DuPont A coalesced phthalooyanine pigment is made by reacting phthalonitrlle with a metal salt such as cupric chloride in the presence of a substantial amount of a calcined TiO pigment as a substratum. The resulting product is sat1sfactoryror use without any further conditioning steps. British patent 455,767 is very close art against this application but has not yet been cited in the prosecu tion, and it appears probable that a patent will issue. However, any patent which issues will probably have little value beyond that of a disclosure. The process is that formerly contemplated for use at Newark in the manufacture of Pigment BXrCR. , 2. Phthaloeyanine Greens U.S. 2,195,984, issued 4-2-40 to Dent and Sylvester of I.C.I, Phthalooyanine pigments may be chlorinated or bromiaated in hot molten phthalic anhydride using elementary chlorine or bromine. Although this is the first published patent on the process of halogenafcing a phthaloeyanine pigment, it does not bear the earliest application date. U.S. 2,214,469, issued 9-10-40 to Linstend and Dent of I.C.I* This patent has a broad claim to the process of halogenating a phthaloeyanine and discloses the us of a number of halogen carriers including aluminum chloride and sulfur chloride. This patent has the earliest application date of any patent on the direct halogenation of phthaloeyanine but lost out as to the presently preferred product in an interference with U.S, 2,276,860 because it did not contain adequate DUP050150245  9 ~ disclosure of the degree of halogenation necessary for the preferred phthalocyanine green. U.S. 2,247,752, issued 7-1-41 to Fox of DuPont This patent covers the aluminum chloride/sodium chloride eutectic melt process for the halogen&tion of phthalocyanine p5,gments. It is the process currently used by Orchem but is not contemplated at present for use at Newark. U.S. 2,253,560, issued 8-26-41 to Detrick and Johnson of DuPont. This patent covers the successive steps of synthesis from phthalonitrile in the presence of sodium chloride, mixing the reaction product with anhydrous aluminum chloride and chlorinating directly with out any intermediate purification steps. Th process is not contemplated for use at Newark. U.S. 2,276,860, issued 3-17-42 to Niemann, Schmidt, Muehlbauer & Wiest, assigned to General Aniline This patent has very broad coverage of halogens.ted phthalocyanine containing more than eight halogen atoms per molecule obtained by direct halogenation. It has both product and process claims. This patent issued following an interference with U.S, 2,214,469 mentioned above and is unquestionably a dominating patent in the field. However, the Interference was settled on the basis of royalty free cross licenses between General Aniline and DuPont and we are free to manufacfrire the product. U.S. 2,377,685, issued 6-5-45 to Fox & Jackson of DuPont This patent covers the process of chlorination of phthalo* cyanine pigments by the use of sulfur dichloride, followed by recovery of the sulfur dichloride by sweeping with chlorine gas which reacts with the sulfur monoohloride formed during the chlorination with re generation of the sulfur dichloride. This is the process contemplated for the manufacture of phthalocy^Alne greens at Newark, 3. Metal Free Phthalocyanine Attention is called to references to the manufacture of metal free phthalocyanine in some of the basic patents mentioned above. For instance, U.S. 2,000,051 discloses the deavetsllizafeion of magnesium phthalocyanine and U.S. 2,197,459 discloses the demetallization of tinphthalocyanine. loth of these processes have been used in the past aad the second is currently contemplated for use by I.C.I. The following patents more specifically cover the manufacture of mafcal free phthalocyanine U.S. 2,116,602, issued 5-10-38 to Heilbion, Irving & Linsfcead of I.C.I. This patent covers the process of forming a metal free phthalo cyanine by heating phthalonitrile with alkali metals or their compounds, ammonia or certain tertiary organic bases. It is understood that this DUP050150246 10 - process is highly inefficient. IX.S. 2,155,054, issued 4-18-39 to Lowe of I.C.I. In a modification of the previous patent phthalonitrile is heated with an ethanol amine to form a metal fres phthalocyanine. U.S. Application, Serial #579,332, filed 2-22-45 by Palifeer & Gross of DuPont Metal free phthalocyanine may be mad by reacting phthalonitrile, a solid Inart 5r diluent such as sodium chloride or titanium dioxide and a solid., alkaline agent such as calcium oxide in the presence of small amounts of meth^L glucamin at a temperature of about 200 C. When the reaction is carried out in the presence of a water soluble agent as HaCX and under conditions whereby sc: grinding action occurs during the reaction, such as in a rotary baker, little if any condition ing of the final product other than extraction of soluble impur-. ties is needed. It is believed that this process is currently being* practiced by Orehem but is not contemplated at present for use at Hswark. 4. Finishing Steps U.S. 2,138,049, issued 11-29-38 to Vesce of Hermon A water immiscible organic liquid euoh as toluene ;`.s added to a pigment slurry which is then stirred to emulsify the liquid and the whole dried at a temperature below the boiling point of water to give a dried pigment of improved texture. There Is specific disclosure of the application of this process to phthalocyanine pigments and it has been rather broadly interpreted as covering any process la which a water immiscible organio liquid is intimately mixed with a pigment slurry be fore drying. This patent is included ;ist- a cross licensing agreement tinder negotiation' between DuPont and Harmon and is accordingly avail able for our use Mien negotiations are completed. U.S. 2,173,699, issued 9-19-39 to A.Siegel of DcPont t This is. the patent covering our 'Tftemapo" Blue pigment and covers broadly a water insoluble phthalocyanine pigment Intimately associated with an alkaline earth roslnate* Slice this patent was In cluded in the DuPont/General Aniline agreement on. phthalocyanine, it has been considered as available to all purchasers of phthalocyanine paste from General and no attempts have been made t o enforce it by DuPont, alfeho It is believed that all large scale manufacturers of phthalocyanine pigments have practiced the process. U.S, 2,215,693, Issued 9-3-40 to Davies, Hailwood and Todd of I.0,1, Shis patent covers the use of the sodium salt of the formaldehyde condensation products of naphthalene Sulfonic Acid (Compound #8) In the acid-pasting step of finishing phthalocyanine pigments. There is a product claim to the combination of the pigment and the condensation product without limits to the method of manufacture and there are broad DUP050150247 11 process claims to the precipitation of an acid solution of phthalocyanine in the presence of a water soluble non-hygposoopic disparsi ng agent. There Is disclosure of ball milling in vator and in the presence of the dispersing agent after acid pasting to get further particle size reduction. This patent may be sufficiently broad to cover some of our products but it is probably relatively unimportant to us, U.S, 2,268,144, issued 12-30-44 to Vesoe of Harmon This patent is similar to U.S, 2,136,049 but differs in that a definite emulsion of the'volatile oil is separately prepared and added to the pigment slurry, followed by stirring until the emul sion breaks, after whloh the slurry is filtered and then dried. The process is disclosed and specifically claimed as applied to copper phthalocyanine as well as being claimed broadly. This patent is also included in the cross license agreement with Harmon and is available to our use .when negotiations are completed, U.S. 2,305,379, issued 12-15-42 to Detrick & Lang of DuPont This patent covers Graham*s use of the so-called T3AGig ester in the manufacture of a soft powder phthalocyanine pigment. The claims eover pigment particles coated with the insoluble reaction product of a poly-alkanol amine with a higher aliphatic acid. ,, The process is specifically applied to phthalocyanina pigments by using the agent to emulsify an organic liquid such as toluene in a process essentially similar to that of Harmon in the preceding patent. It is entirely possible that our products may come within the claims of this patent. U.S. 2,327,472, issued 8-24-43 to Vesce.& Sfcalger of Hartaosa A non-flocculating copper phthalocyanine is made by in corporating therein in the wet state a major proportion of aluminum benzoate as a substratum. The disclosure of this patent Is quite accurate and products of this type have been marketed by Harmon but they are believed to be fundamentally high in cost and not a sort ous threat to our business. However, the goal is faisjjhly desirable and, at present, no other good solution is known. U.S. 2,402,167, issued 6-18-46 to Lang Sc Detrick of DuPont This patent is an attempt to cover Orchera' s salt-milling process for finishing phthaloeysnine pigment s. Because of very close prior art the claims are limited to a process using more than four parts of a water soluble salt per part of pigment and to the use of an apparatus which grinds by attrition and shearing as distinguished from impact. It is doubtful if this patent has more than a publication value. * 1; DUP050150248 '* --rr--. 12 U.S. Application, Serial #664,434, filed 4-23-46 by Robbins of DuPont l-napbtbalene' sulfonio acid is added to (or formed in situ) the sulfuric acid solution of a phthalocyanine pigment prior to drowning to give a soft-textured pigment. The agent is used in amounts of from 1 - 2-1/2 times the weight of the pigment. The true significance of this process is not clediy at present but it is not now contemplated for use at Newark. \ British Patent 569,402* issued 5-22-45 to Kollllott and Todd of I.C.I. This is I.C.I,* a salt milling patent and includes a ftmw.il quantity of a fatty acid or ester thereof with the salt. The preferred procedure .uses anhydrous sodium sulfate with a small amount of oleic or linolelc acid. B. PATENTS OP LESSER IMPORTANCE 1. Synthesis of Copper Phthalocyanine U.S. 2,000,052 - I.C.I. - covers the reaction of phthxLimide with a metal in the presence of ammonia,, - U.S. 2,076,043 - I.C.I* - CPC is formed by reacting an orthohalogen benzamld with cuprous cyanide. U.S, 2,124,742 - I.C.I. - Copper phthalocyanine may be formed by heating a matal-free phthalocyanine with copper or copper salts. U.S. 2,138,413 - Interchemical - A pigment which does not need acid pasting Is prepared by reacting phthalonitrile and copper salts In the presence of aliphatic &i** or trlhyarlc alcohols or alcohol poly ethers. U.S. 2,153,300 - DuPont - The violently exothermic reaction between phthalonitrile and the copper salts is controlled by adding the reactant port 5.on-wise to the rotary baker. \ U.S. 2,154,912 - General Aniline - Phthalonitrile is boated with a-metallic cyanamid to form a phthalocyanine pigment. '> U.S. 2,160,837 - DuPont - Phthalonitrile and metallic copper \ may be caused to react at a temperature of 16C~170C in the presence of small amounts of chloride of amphoteric metals or ammonia. US. 2,166,213 -- I.C.I. - This is the basic patent for the reaction of phthalonitrile with a copper produolug agent to for* copper phthalocyanin. U.S. 2,194,250 -- Interchemical -- This covers on apparatus for the manufacture of phthalocyanine pigments by the reaction of phthalo nitrile vapors with a polished metal surface. DUP050150249 ( / 13 U.S. 2,202,632 - I.C.I, - Ortho-arylcue di "cyanides are heated with a compound of a metal of the aocond group of the periodic table. 0*3. 2,212,924 - General Aniline -- Phthalonitrlle is heated with an amide am & metal salt* /U,S, 2*216,761 - I.C.Z. - Covers the us of ammonium sulfamat as a catalyst in the phthalic anhydride/urea proeess* yCS./s,216,867 - I.C.I. - Covers broes 13 y the use of amino sulfonic acid in place of urea in the manufacture of phthalccyanine. /U.3^ 2,216,868 - I.C.I. - Covers the use of ammonium sulfamat in place of/`urea in the phthalic anhydride process for cobalt, nickel or iron phtialocyanina. U'JS. 2,242,301 - I.C.I. - la a belated issuance of one division, of the basic patent for heating phtbalonitrlle with a copper salt and involves/the use of a neutral organic solvent . / TJ.S. 2,245,098 - Interchemical - Covers the reaction of phthalonitriles vapors with a polished metal surface followed by scraping off the plgmenp jthus formed* / 1 U.S. 2,276,598 - S.C.I* - The presence of small amounts of HaOH, CaO or EfagOOg improves the efficiency of the reaction between phthhlonitrlle and metal compounds in the presence of liquid diluents. ' ! U.3. 2,302,612 - American Gyanamid * Chlorine-free CPC is prepared from phthalonitrlle And cupric chloride by reacting in the presence of anhydrous ammonia*. C.S, 2,318,783 - American Cyanemid - Chlorine-free CPC is prepared by reacting phthalonitrlle with enhydroue copper sulfate In the 'presence of nitrobenzene and anhydrous ammonia under pressure. TJ.S. 2,318,787 - American Cyanamid Also covers the reaction of phthalonitrlle with cupric sulfate in.the presence of sisr-jonia. U.3, 2,375,780-- Jaterchemical - Phthalocyanines nay be pre pared by heating phthalic anhydride, ammonia and a metal salt of cyanuric acid. TT.3, 2,382,441 - Interchemical - Phthalonitrlle aad metal compounds are reacted in the presence of such limited quantities of hydroxy aliphatic solvents that the major portion of the solvent is evaporated during the reaction. 1. . DUP050150250 14 US Application, Serial #403,866 ~ APC - Benzols acid and related compounds are effective in preventing the foaming of a phthalic anhydride/urea fusion synthesis. In listing the following British patents, those patents which have substantially equivalent U.S. disclosure have been, for the most part, omitted, British 382,169 * Scottish Dyes (I.G.I.) - Shis is the first disclosure of phthaloeyanines la English and covers a process in which ammonia is passed into molten phthalic anhydride in the presence of a metal to give a blue solid which may be purified by precipitation from sulfuric acid. British 453,767 - 1.8. - Phthalonitrile is heated with metals or metal compounds taking part in the formation of the dyestuff in the presence of an oxide or salt of a metal of groups. .1 to 4 .of the periodic system.which salt is solid at the reaction temperature and inert and is used as a diluent. This is the beat prior art against our Pigment BX-CR process, but there is no -3. equivalent. British 457,786 - I.C.X. - ABsnonitBK phthalate or Its deri- " vatives may be heated with a metal salt in the presence of an amino sulfonic acid to give a' phthalocyanine, British 458,754 - I.G. - Phthalonitrile and copper salts are heated in the presence of tertiary bases under special conditions of pressure and concentration. British 459,780 * X.G. ** A high boiling diluent other than a tertiary base is added to the process of the preceding patent. British 462,839 - X.G. - Phthalonitrile is heated with metal amides or eyanamldea together with high molecular weight alcohols or mereaptana. British 482,387 - X.G. ~ Phthalonitrile is heated with metal compounds in. the presence of diluents free from nitrogen and hydroxyl groups but under pressure. British 503,029 - Hcnteoatlni - Phthalic anhydride and copper compounds are heated in the presence of &i~cyano-dismides. British 552,124 - DuPont - Covers the use of infra-red heating in the phthalonitrile process for phthalocyanine. The TT.S. application has bean finally rejected. 2. Phthalocyanine Greens U.S, 2,227,628 - DuPont - Phthaloeyanines may be fluoridated by treatment with fluorine in liquid hydrogen fluoride. British 470,079 * X.G. - Simultaneous Mogenation and formation of the phthalocyanine by heating phthalonitrile with the halogenating DUP050150251 15 - agent In the presence of the metal halide. British 499,415 - 1.6. - Copper phthalocyanine may be chlorinated with, chlorine gas in triohlorbenzene in the presence of antimony trlsulfide under atmospheric pressure. British 500,471 - 1.0. ~ Phthalocyartisaes are h&logenated in the presence of organic acid halides arid with halogen carriers. 3. Metal Pfree Phthalocyanines U.3. 2,153,630 - I.C.I. - Phthalonitrile is heated in an atmosphere of aimaonia*, 6.5, 2,182,763 - General Aniline ~ Fiathalonitrile is heated with sodamide and dimethyl aniline in the presence of aliphatic alcohol. U.S. 2,214,454 - I.C.I, - An al&ali phthalocyanine is treated with methyl alcohol and then diluted with water tc give & mstal-free phthalocyanine superior to that frost acid pasting. British 476*168 - 1.6. - Phthalonitrile is heated with phenols or naphthols. British 480,249 ** 1,6. - Phthalonitrile is heated with a Grignard reagent and hydrolyzed with sulfuric acid to give a metal-free phthalocyanine. 4. Other liletal Phthalocyanines Many metal phthalocyanines other than copper are disclosed in a number of the patents listed above but the following patents are limited to certain other metal phthalocyanines. tr.S. 2,056,944 - I.C.I. Covers lead phthalocyanine. If.3. 2,124,419 - I.C.I. " Covers iron, nickel or cobalt phthalocyanine prepared from phthalonitrile. TJ.S. 2,155,038 - I.C.I, - Covers vanadyl phthalocyanine. 50 Miscellaneous Finishing Methods 6.5. 2,192,704 - DuPont - Covers cc-aeid pasting of two or more phthalocyanines. 9.3. 2,225,302 - Inierchsmical - Covers the formation of CPC sulfate by careful dilution of the sulfuric acid solution. U.S. 2,238,243 - DuPont - Covers a sen stable blue paint con taining alumina hydrate and the barium lake of eulfonafced CPC. DUP050150252 16 U.S. 2,238,275 - DuPont - Covers the precipitation of any soluble dispersing agent prior to the addition of the oil in a pigment flushing operation. U.S. 2,276,175 - Allied Chemical & Eyo - Covers the treatment with a mild oxidizing agent as laOCl after acid pasting. U.S, 2,282,006 - DuPont - Covers th uso of cation active agents plus volatile water immiscible organic liquids In making soft, dry pigments including phthalocyanlne. DoS. 2,282,303 - DuPont - Covers the use of nitrogen bases to improve texture* U.S. 2,284,685 - DuPont - Is another patent on the isolation of CPC sulfate as a step in the acid pasting procedureB U.S. 2,291,452 - DuPont ~ Covers drowning CPC from solutions in acids in the presence of lauric acid and the like. U.S. 2,334,812 - DuPont - Covers turbulent flow drowning of an acid pasted phthalocyanlne ,, U.S. 2,359,737 - American Cyansmid ** Covers drowning sulfuric acid solutions in water in the presence of an inert water immiscible organic liquid not sulfonated. U.S. 2,365,464 - DuPont - Another patent on the isolation of the crystalline CPC sulfate. U.S, 2,367,519 - Sherwin-Williams - Covers boiling the pigment suspension resulting from the drowning of m acid pasted phthalocyanlne British 454,858 - I.G. - Covers -drowning a sulfuric acid solution of a phthalocyanlne in the presence of a dispersing agent and either in the presence of a substratum or under conditions which will simultaneously form a substratum. British 466,042 * I.G. - Covers broadly the mixing or billing of a phthalocyanlne with dispersing agents in the presence of water. British 475,882 - I.G. - Is similar to the preceding patent but applied to a metal-free phthalocyanlne. British 502,623 - Montecatini - Phthalocyanlne pigments are converted to the sulfate with sulfuric acid below 903 in strength and then hydrolysed with water. British 503,666 - I.G. - CPC is treated with 78,3 sulfuric acid at 45C and then with water to give soft powder. British Application 5721 - 1944 - American Cyanamid - Halogen free phthalocyanlne pigments are acid pasted, exposed to a crystallizing solvent, then salt-milled to the desired fineness and again exposed to the solvent. The product has 70,a the strength of the acid pasted 6 DUP050150253 .ZV^Vv^ - 17 - material but no longer grows crystals in the solvent. Reference is made to two crystal forms of CPC. The crux of the invention seems to be an implication (without a definite statement) that, if crystals which have been grown- in solvent are mechanically reduced in size,, no farther growth in crystals will occur. JTo U.S. equivalent of this patent has appeared although, it was filed trader convention in England. 6* Use Patents U.S. 2,167,514 - X.C.X, - Phthalocyauiaes in a rubber dispersed master batch. U.S. 2,168,576 - General Aniline - Vulcanized rubber colored with phthaloeyanin colors. U.S. 2,192,705 - X.C.X. - Rubberized fabric colored with CPC. U.S. 2,517,571 - Xnterchsmieal ** Ua of phthalocyarlnes in pi@aent printing using a liquid volatile pine terpen to avoid crystal growth* U.S. 2,539,789 - I.C.I.- Impregnating a fiber with a diaao of an amino phihaloeyaniae and developing with a coupling component. I U.S. 2,339,740 - X.C.X, ~ Impregnating a fiber with a diazo of a poly-amino phthaloeyanin aid decomposing to deposit insoluble phthalo- cyanine. British 435,614 - X.C.X, - Use of phthalocyanlnea in nitro cellulose coating compositions. 7. Substituted PhthalocvaEin.es U.S, 2,099,689 - Oqher&l Anilir. - Water insoluble metal salts of phthaloeyanin sulfonic acid. U.S. 2,099,690 - Geheral Aniline - lakes of th water insoluble salts of phthaloeyanin sulfonic acid. U.S, 2,116,196 - General Aniline - Acylated phthalocyaaine. U.S. 2,117,720 - General Aniline - Phbhalonltriie is reacted with benzanthrone and alumirfaa chloride to give a vivid groan dyestuff. U.S. 2,122,137 - General Aniline - Alkyloxy and aryloxy phthalocyanine , U.S, 2,124,299 - General Aniline - Halogenated phthalccyanines react with organic hydroxy eofcpounds to form an ether type derivative. U.S. 2,133,340 - General Aniline - Acyl amino phthaloeyanin. U.S. 2,135,633 - General Aniline - Dyeing textiles with phthalo- cyanine sulfonic acid. ' DUP050150254 18 - U.S, 8,150,741 * I.C.I. - A quaternary ammonium salt of a poly sulfonated metal phthalocyanin. U.S. 2,165,768 - DuPont - Phthalccyanines are formed directly on the surface of a metal body to cover tbs same. U.S. 2,166,240 - I.C.I. - A compound similar to phthaiocyanlna but with CE - group in place of a U r in the large ring* U.S. 2,187,816 - General Aniline - Covers the reaction product of phthalocyanin sulfonic acid with organic bas5.e expounds. * U.S. 2,197,860 - General Aniline - PhthaXocyanines containing an oxazol, thiaaol, or iaidazol group on the benzene nuclei. 17*3* 2,815,517 - General Aniline - A CPC containing a phenyl group as a substituent on each of its four benzene nuclei. U.S, 2,215,720 * I.C.I* - Phthalocyanines containing three earboxy groups. U.S. 2,225,441 ** General Aniline - Covers phthaiocyanlna con taining triehlor-methyl groups in the nuclei. U.S. 2,242,469 - General Aniline - Covers a phthalocyanine con taining both a phenyl group and a earboxy group In each benzene nucleus. U.S. 2,266,404 - General Aniline - Covers a metal phthalocyanin with both a sulfonic acid group and a naphthylamino group In each benzene nucleus. U.S. 2,276,918 - General Aniline - Covers- a metal phthalocyanin in which each benzene nucleus contains both a sulfonic acid group and an alkoxy or aryloxy group. U.S, 2,277,588 - I.C.I. ~ Covers tetra-pyridyl phthalocyanines. U.S. 2,277,628 - I.C.I* - Covers, quaternary salts of tetrapyridyl phthalocyanines . U.S, 2,277,629 - I.C.I., - Covers pyridyl phthalocyanines. U.S. 2,280,072 - I.C.I. - Covers fcetra-smino-phthalocyanines. U.S. 2,280,507 - General Aniline - Covers a sulfonated phthalocyanine obtained by sulfon&ting a phthalocyanin containing a phenyl group on each benzene nucleus. U.S. 2,285,359 - General Aniline - Covers sulfonated phthalooyanines obtained by synthesis from sulfonated phthalic acid. DU P050150255 - 18 - U.S, 2,150,741 - I.C.I, - A quaternary ammonium salt of a poly sulfonated metal phthaL ocyfinine,, U.S. 8,165,768 - DuPont - Fhthalccyanines are formed directly on the surface of a metal body to cover the same. U.S, 8,166,240 - I.C.I. - A compound similar to phthalocyanine but with CH - group in place of a H in tbs largo ring. U.S. 2,187,816 - General Aniline Covers the reaction product of phthalocyanine sulfonic acid with organic basic ovaapounds. * TJ.S. 8,197,860 - General Aniline - Ihtheloeyanlnes containing an oxazol, thl&zol, or imid&zol group on the benzene nuclei. U.S. 2,815,517 - Genaral Aniline - A CPC containing a phenyl group as a substituent on each of its four benzene nuclei. BUS, 2,215,726 * I.CZ - Phthalccyantnoe containing three carboxy groups. TJ.S, 2,285,441 - General Aniline - Covers phthalocyanine con taining triohlor-methyl groups in the nuclei. TJ.S. 8,242,469 - General Aniline - Covers a phthalocyanine con taining both a phenyl group and a carboxy group In each benzene nucleus, U.S. 2,266,404 - General Aniline * Covers a metal phthalocyanine with both a sulfonic acid group and a naphthylamino group in each benzene nucleus. U.S. 2,276,918 - General Aniline - Covers-a metal phthalocyanine in which each benzene nucleus contains both a sulfonic acid group and an alkoxy or aryloxy group. U.S. 2,277,588 - I.C.I. - Covers tetra-pyridyl phthalocyanines. U.S. 2,277,628 - I.C.I. - Covers quaternary salts of tetrapyridyl phthalocyanines. U.S. 2,277,629 - 1,0,1,. - Covers pyridyl phthalocyanines. U.S. 2,280,072 - I.C.I. ~ Covers fcstra-anino-phthalocyanines. U.S. 2,280,507 - General Aniline - Covers a sulforated phthalocysnine obtained by sulfon&ting a phthalocyanine containing a phenyl group on each benzene nucleus. U.S. 2,285,359 - General Aniline - Covers sulfonated phtbalooyanines obtained by synthesis from sulfonated phthalic acid. DUP050150255 19 U.S. 2,886,679 - I.G.I. r Totra~nltro -coppsr phthalocyanlne. U.S. 8,888,478 - General Aniline ~ Phthaloeyanine sulfonic acids are treated with, chior"sulfonic acid. U.S. 8,290,906 - I.G.I. ~ Water soluble sulfonitm derivatives of phthalocyanines. U.S. 2,300,572 - General Aniline - Phthalocyanines contain" ing up to four sulfonamide groups on the benzene nuclei. U.S. 8,343,663 - I.G.I. - Poly-sulfide dyes of the phtbalocyanine series. U.S. 2,342,663 - I.C.I. - A method of preparing copper phthalocyanine containing disulfide groups. U.S. 2,349,089 - X.C.I, - Stabilized diazonium derivatives of phthaloeysnia compounds. U.S. 2,349,090 - I.G.I, - Stabilized poly-diazo phthalocyanines. U.S. g 349,091 - I.G.I, - Stabilised poly-diazo phthalocyanines. U.S. 2,351,318 - I.G.I. - Water soluble dyes are obtained by coupling diazotizsd amino phthalocyanines with coupling components con taining solubilizing groups. U.S. 2,351,119 - I.G.I, - Poly-dlazoniuar phthalocyanines are coupled with pigment coupling components such as beta-naph.th.ol or aceto-acet-snilide to give water insoluble dyes. British 460,152 - I.G. - Covers the preparation of pigments by the precipitation of water insoluble dyes on phthaloeyanin pigments as substrate. British 471,418 - I.G. - Heterocyclic dyestuffs of the phthalooyanlne series are made using di-amino maleic acid dinitrile as a starting ingredient, British 471,435 - I.G. ~ Halogen containing phthalocyanines may react with a primary or secondary amine to give products greener than the original. British 487,261 - I.G, ~ Phthalocyanines may be heated with trichlor-acetio acid and the like to give a halogen containing alkali soluble phthalocyanlne. British 490,744 - I.G, - Gyclic-orbho-dichloro compounds are heated with cuprous cyanide in the presence of an organic nitrogenous base. British 492,177 - I.G. - A phthalocyanlne containing halogen is heated with a mercaptan. DUP050150256 - 20 British 492,194 - I.G. - Pb.thaloni.tr11a Is heated with halides of polyvalent metals in the presence of bases snob as pyridine or quinoline. British 496,663 - 1.6. - fhthalio acid~4-sulfonsmld.es are re acted with copper salts in the presence of urea and with the usual catalysts. British 496,683 - I.G. - Phtbalocyanin.es are heated with aromatic compounds containing halogen in a aide chain to give new compounds. British 496,819 - I.G. - Diphenyl-3-4-dioarboxylio acid con taining a further carboxy group is heated with urea and a metal salt to give a water soluble phthalocyanine. British 514,857 - I.G. - Phth&iocyanin sulfonic acids are treated with halogenatlng agents. The following two German patents are cited as interesting dis closures in the general field without comparable disclosures in English. German 657,688 - I.G. - Discloses combinations of phthalocyanines with other water Insoluble colors obtained by precipitating the second color on the phthalocyanine. The disclosures include Eanea Yellow types. Red 2B, and Chrome Yellow. German 696,592 - I.G* - Copper phthalocyanine is heated with anthraquinone acid chloride to give vatable dyes. DUP050150257